Hydroxylation of acetylenic compounds



Patented Apr. 25, 1944 I r s HYDROXYLATION OF ACETYLENIC COMPOUNDSNicholas A. Mllas, Belmont, Mass assig'nor to Research Corporation, NewYork, N. Y., a corporation New York No Drawing. Application March 16,1942, Serial No. 434,980

6 Claims. (Cl. 260-535) This invention relates to the catalytic oxidapsubstantially anhydrous environment, e. g., in the tion f unsaturatedanic compounds, and it presence of an essentially anhydrous inert or-Prmcipal Object is to provide a simple econom ganic solvent, and of asmall amount of acataand emcient process of producing 159ml lyticallyactive oxide of a metal known to form oxygenated organiccompounds suchas glycols,

. very unstable peracids rather than peroxides, inggegolasidagdehydes,ketones, quinones and Oleluding Os, Ti, Zr Th, v, Nb Ta. Cr, Mo W, UFurther bj will be apparent from and Ru(see J. A. C. 8., 59, pages 2342and 2343;

sideration of the following description wherein and e chte, 41 (1908),page 3536), preferably, 1 have ill t t th application of my new 10osmium tetrao'xide, ruthenium tetroxide, vanadiprocess in thepreparation of various substances um pentoxide, molybdenum oxide orchromium n tit in the Class '1 oxygenated g ic trioxidein an essentiallynon-alkaline environcompounds. ment (that is, in the absence of aninorganic The Present application which is a continua base), there isproduced an oxygenated organic tion-in-part of my application Serial No.382,273,

compound, the nature of which depends upon filed'March 7, 1941, isparticularly concerned with the hydmxylation of members of the group theparticuiartype of unsaturated compound sub of unsaturated organiccompounds which jected to such treatment, the temperature, the

mm the acetylemc linkage which group pressure (it the compound treatedbe in gaseous of compounds includes: acetylene itself mono- Phase), thesolvent medium, the extent of oxidesubstituted acetylenes-of the typetion and other such factors. For example, acetylone and its mono-, ord1-, substitution products yield hydroxy aldehydes and/or hydroxy acids.wherein R represents a monovalent organic radi- The reaction of theacetylenic compounds and and disubsfimwd acetylenes of the type hydrogenperoxide may be illustrated by the fol- R-CEC-Ri lowing equations:

' Moaosubstituted acetylene (1) catalyst-{ on on RCECE +noon -i n aRC-CH 21110 a H AH 0 4% catalyst RC=CH o R I CII H I! OH 0 wherein Rrepresents a monovalent organic radical o! the group consisting of alkyland aryl radicals.

wherein R and R1 represent monovalent organic 40 radicals.

I have found that when an unsaturated organic compound containing theacetylenic linkage is may be oxidized further to produce organic acidstreated with hydrogen peroxide, in an initially as follows:

( H H (c) H 4} -catalyst catalyst R --('?H HOO H B -COOH H1O RC-n HOOH-0 RC-COOH H O H O H Disubstituted acetylene (a) catal 0H 0H 1 ae is 5 vI to! t H H ea The hydroxy and keto aldehydes thus formed wherein R1 andR: represent monovalent organic of acetic acid and a tertiary alcohol;or, the subradicals of the group consisting of alkyl and arylstantially-anhydrous CrOs may be added directly radicals. in the solidform to the, substantially anhydrous The reaction of hydrogen peroxideand acetylmedium containing hydrogen peroxide and the one (Cal-I2) toproduce (a) glyoxal and glycolllc 5 substancetobehydroxylated.Preparation of the aldehyde, (b) glycollic acid, and (c) oxalic acidother catalytic metal oxides may similarly be may proceed asfollows: vformed by dissolving the metal oxide in one or (a) eitolysw on on noonHCECH noon -t n n HC-C-H 211,0

' a (ti: catalyst In carrying out my process successfully, it is anotheroi the organic solvents above stated. 0r,

advisable to employ, as media for the reaction, the selected catalytic ml xide may be added.

substantially anhydrous solvents, preferably sein p e o finely dividedtat to t hy olected from such organic substances that do not genperoxide rea n wherein the same eventuundergo oxidation duringthereaction. Tertiary dissolves forming a comp e y e us alcohols ingeneral, and particularly tertiary buol Th ta yst may be used alone orin tyl and tertiary amyl alcohols, have been found m in ion.

to be suitable solvents for this purpose, although I e found that thetemperature Plays an it is to be understood that the invention is notimportant role in directing the yp of oxy nconflned to these solventssince various other re- 80 died Product to be For pl f ragents, such asnitriles and certain types or ethmation of gly l in h yields is usuallyf ers, acetic acid-tertiary alcohol mixtures, etc., vored between room pt e e. a. 1 C.

may b used t advantage, m t u of oper... and several degrees below 0 0.,whereas aldeable nitriles is acetonitrile. Illustrative examhydes. ke nn Organic acids e produce ples of operable ethers include: ethyl,propyl, r advantageously at t mp hi butyl and amyl dioxane, ethers ofethylene glythan room mp r re eg.. between 21 C. 1 d diethylene glycol mAmong operable and the boiling point of the non-aqueous solvent inert(that is, unreactive) organic solvent media ployed).

is nitromethana 'Ihe organic solvent employed The following examples areiflustrative Of the is, in all cases, strictly a medium or vehicle, and40 applicatmn 0f the invention! is 110? a reactant 1. Gaseous UnslmmarrnSuss'rmca The reaction mixture (material to be oxidized. the hydrogenpemnde treating agentthe organic For the production of ethylene glycolor of solvent medmm where used and the catalyst) any glycol from anyunsaturated gaseous subpregembly is mmany substantially anhydmus stance,the latter maybe bubbled through the A preferred procedureior thepreparation oi Pemxide reif'gent rimming any One of the th hydrogenperoxide reagent in tertiary butyl alysts above suggested. or anycombination of alcohol is as follows: them, or it may beintroducecLunder pressure of 400 f pure tertiary b alcohol is addedvarious magnitudes from one to several atmosto 100 cm of 30% hydrogenperoxide (Albone C) pheres or even several hundred atmospheres.

' and the solution treated with small portions oi The end the is usuallyindicated by anhydrous sodium p t forming t a color change or thecomplete utilization Of layers. The alcohol layer, containing most ofthe peroxide as determined by titration- The the hydrogenperoilide,isremoved. The so sepother pmducts may be separated b rated hydrogenpi6xide flch layer may be used fractionation or in any other suitablemanner. without further treatment; however, I may fur- 55 2. Lrqum ANDSou Unsamam S'uns'rmcrs ther dehydrate the same by treating it with moreanhydrous sodium sulphate, and finally with anhydrous calcium sulphateor magnesium 5111- The unsaturated hydrocarbons are dissolved phate. Asolution containing approximately 6% 0r mixed with the peroxide reagentainin hydrogen peroxide in tertiary butyl alcohol is o a suitablecatalyst or the type previously sugthus obtained, and this solution maybe concensested n the reaction is allowed to proceed .trated by vacuumdistillation of the alcohol at eit e at or below room temperature i syeols room temperature to any desired concentration are desired, orabove room temperature it alde-' without loss 0! the peroxide, providedan allhydes, ketones, and organic acids are de ired.

glass or other suitable apparatus is employed. The hydrocarbons m y bePr sent preferably in An osmium tetroxide catalyst may be prepared 1 theratio of one mole to one or two moles o t by dissolving substantiallyanhydrous osmium peroxide, althou h greater excess of peroxide istetroxide in substantially pure tertiarybutyl al.- neeessary whenaldehydes, ketones and acids are cohol, tree from isobutylene. desired.The speed or the reaction up to certain A chromium trioxide catalystsimilarly maybe limits dep n p h con entration of the catprepared bydissolving substantially anhydrous alyst which may be present preferablyin conchromicacld (CrOi) in a substantially ur satcentratlons from .05g. to .5 g. per mole f t united tertiary aliphatic alcohol (Carlin-+1):COH, substance to be oxidized, although it is to be une; g.,substantially pure tertiary butyl or amyl derstood'that these limits mayat ti alcohol, or in a substantially anhydrous mixture 76 eeeded withoutafleoting appreciably the yields of the oxygenated products. The end ofthereaction is usually indicated by a color change or by the absence ofperoxide. The glycols or other oxygenated products may then be separatedeither by fractionation or in any other well known manner.

In preparing glyoxal from acetylene by the present iplOCESS, 1 mole ofacetylene is reacted with 2 moles of hydrogen peroxide by bubbling theacetylene through an initially substantially anhydrous solution ofhydrogen peroxide in substantially pure tertiary butyl alcoholcontaining osmium tetroxide dissolved therein, while maintaining thereaction mixture at normal room,

temperature (1. e., a temperature of about 20-21? C.). The course of thereaction is believed to be as follows: at first the compound OH OH Forpreparing glycollic acid from glycollic aldehyde, 1 mole of the latteris reacted with 1 mole of HOOH, in the form of the hereinbefore referredto peroxide reagent, at normal room temperature.

Oxalic acid is prepared from glyoxal by reacting 1 mole of the latter,at room temperature, with 2 moles of HOOH (in the form of peroxidereagent) In the same manner, 1,2,4-trihydroxy-butanone-3 e is producedby reacting 1 mole of vinyl acetylene, H2C=CH-CECH, with an amount ofmroxide reagent corresponding to 2 moles of. hydrogen peroxide, at atemperature of about C. with excess of HOOH, it is possible to form fromthe vinyl acetylene the unstable compound OH OH HOCHr-(F--CHrOH whichlatter, losing compound HOCH2-(|]-C]-CHIOH Illustrative of theapplication of the present hydroxylation process to an hydroxy acetylenecompound is the following:

Equimolecular quantities of the peroxide reagent (with either vanadiumpentoxide or oswater, is converted to the mium tetroxide as the catalystcomponent) and acetylene carbinol,

are caused to react at normal room temperature, whereby there isproduced 2-methyl-2,4-dlhydroxy-butanone-(i,

- HIC It is believed that in the course of this reaction the initialhydroxylation product is the compound which compound rearranges to yieldthe 2-methyl-2,4-dihydroxy-butanone-3.

By reacting equimolecular quantities ofthe peroxide reagent (with osmiumtetroxide as the catalyst component) and tetramethyl acetylene glycol,

CH: i

at normal room temperature or below, it is assumed that the initialhydroxylatlon product is the compound which latter rearranges to formthe recoverable final product, 2,5-dimethyl-2,4,5-trihydroxyhexanone-Zi,

inc CH: \n H |l mo 0H 0 $11 on:

However; with excess of the hydrogen peroxide and by reacting at higherthan room temperature, there may be produced the unstable compoundwhich, under the conditions of reaction, tends to split up to yield 2moles of Z-methyl-Z-hydrompropionic' acid (or, alpha hydroxy-isobutyricacid).

As another example, a-hydrow-butyne,

HaO-CHOH-CsCH when reacted with an equimolecular amount of the peroxidereagent (using osmium tetroxide as the catalyst component), at normalroom temperature, yields as an initial hydroxyiation prodnot theunstable compound n mo-to==.=on

n n n which latter rearranges to give as final productzA-dihydroxy-butanone t,

' mo-E-w-omon a I Similarly treated, the starting material2,4-dihydroxy-hexyne-3 1 H H HflJ-C-CEC-C-UH:

H H initially yields the unstable compound which latter rearranges togive as final product 2,4,5-trihydroxy-hexanone-3,

on in in Iclaim:

1. Process of producing polyhydroxy derivatives of unsaturated organiccompounds characterized by containing a triple bond between two adjacentcarbon atoms, which comprises treating the acetylenic compound withhydrogen peroxide in a non-alkaline and initially substantiallyanhydrous environment, in the presence 01 a catalytically active oxideof a metal'which forms unstable peracids, and recovering a polyhydroxyderivative of said acetylenic compound from the .resulting reactionmixture.

2. Process of producing polyhydroxv derivatives of acetylenic compoundsof the formula in which R1 and R: represent monovalent substituents ofthe group consisting of hydrogen and aliphatic and aromatic radicals,which comprises treating the acetylenic compound with hydrogen peroxidein a neutral and initially substantially anhydrous environment, in thepresence of a catalyticaliy active oxide of a metal whichforms-unstable'peracids, and recovering a po y droxy derivative of saidacetylenic compound from the resulting reaction mixture. I

3. Process of pro ucin p lyhydroxy derivatives 0i acetylenic compoundsof the formula in which R; and Ra represent monovalent substituents o!the group c of hydrogen and aliphatic and aromatic radicals, whichcomprises treating the acetylenic compound with a nonalkaline andinitially substantially anhydrous solution oi! hydrogen peroxide in aninert solvent 6 medium, in the presence of a catalytically active oxideof a metal which forms unstable peracids, and recovering a polyhydroxyderivative of said acetylenic compound from the resulting reactionmixture.

l0 4. Process of producing poly droxy derivatives or. acetyleniccompounds of the formula R1-CEC.R2 in which R1 and R: representmonovalent substi- 15 tuents of the group consisting of hydrogen andalkyl and aryl radicals, which comprises treating the acetyleniccompound with'a neutral and ini-;

tially substantially anhydrous solution of hydrov gen peroxide in aninert organic solvent medium 2'0 consisting essentially of atertiarymonohydric saturated "aliphatic alcohol, in the presence of acatalytically active oxide of a metal which forms unstable peracids, andrecovering a p lyhydroxy derivative of saidacetylenic compound from the25 resulting reaction mixture.

5. Process of producing a polyhydrox derivative o1 acetylene. whichcomprises treating the acetylene with hydrogen peroxide ,in a neutraland initially substantially anhydrous environ- 30 ment, in the presenceof a catalytically active mcnoms A. mas.

